CN112831026A - Synthetic method of aliphatic epoxy resin - Google Patents
Synthetic method of aliphatic epoxy resin Download PDFInfo
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- CN112831026A CN112831026A CN202011630222.3A CN202011630222A CN112831026A CN 112831026 A CN112831026 A CN 112831026A CN 202011630222 A CN202011630222 A CN 202011630222A CN 112831026 A CN112831026 A CN 112831026A
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- CN
- China
- Prior art keywords
- epoxy resin
- cyclohexene
- aliphatic epoxy
- dicarboxylate
- synthesizing
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- 239000004844 aliphatic epoxy resin Substances 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title abstract description 8
- OVHKECRARPYFQS-UHFFFAOYSA-N cyclohex-2-ene-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC=C1 OVHKECRARPYFQS-UHFFFAOYSA-N 0.000 claims abstract description 83
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000002085 enols Chemical class 0.000 claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- 150000005690 diesters Chemical class 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 32
- -1 maleic acid diester Chemical class 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000006172 buffering agent Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 68
- 239000003822 epoxy resin Substances 0.000 abstract description 15
- 229920000647 polyepoxide Polymers 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006735 epoxidation reaction Methods 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000003112 inhibitor Substances 0.000 description 13
- 239000011964 heteropoly acid Substances 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000001308 synthesis method Methods 0.000 description 7
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 6
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 239000000872 buffer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical group 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Abstract
The invention relates to the field of epoxy resin, in particular to a synthetic method of aliphatic epoxy resin, which comprises the steps of (1) reacting conjugated olefin with maleic diester to obtain cyclohexene dicarboxylate; (2) reacting cyclohexene dicarboxylate with enol to obtain cyclohexene dicarboxylate; (3) under the action of hydrogen peroxide oxidation, cyclohexene dicarboxylic acid dialkene ester is used for obtaining the aliphatic epoxy resin. The synthetic method starts from the reaction of conjugated olefin and maleic diester, the obtained cyclohexene dicarboxylate and enol have few by-products in the reaction process, and meanwhile, the concentrated sulfuric acid does not exist, so that the corrosion of the concentrated sulfuric acid on equipment is avoided, the reaction is mild, hydrogen peroxide is used for oxidation in the subsequent epoxidation process of the cyclohexene dicarboxylate, the by-product is water, and the method is clean, environment-friendly and easy for industrial production. The epoxy resin obtained by the synthetic method has good weather resistance and can be used for outdoor paint.
Description
Technical Field
The invention relates to the field of epoxy resin, in particular to a synthetic method of aliphatic epoxy resin.
Background
Epoxy resins are widely used because they have a range of excellent mechanical properties. The epoxy resin is a substance with various forms from liquid to viscous and solid, has little independent use value, and has application value only when reacting with a curing agent to generate an insoluble infusible polymer with a three-dimensional network structure, so that the epoxy resin belongs to thermosetting resin. The epoxy resins are classified into low molecular weight epoxy resins, medium molecular weight epoxy resins and high molecular weight epoxy resins according to their molecular weights. The low molecular weight epoxy resin has a softening point less than 50 ℃, a polymerization degree less than 2, can be dissolved in organic solvents such as ketones, ether alcohols and the like, has higher storage stability without a curing agent, can not be cured by heating, has good mechanical properties after crosslinking curing, resists acid and alkali corrosion, has small curing shrinkage, high insulating strength, but has larger brittleness, low impact strength and poor weather resistance, and is not suitable for being used as outdoor coating.
At present, most of epoxy resins in China are bisphenol A type epoxy resins, and the weather resistance is poor due to the fact that a large number of aromatic ring structures are contained in a molecular structure. There is a great deal of interest in developing outdoor epoxy resins having excellent weatherability and good processability. Based on this, 4, 5-epoxycyclohexyl-1, 2-dicarboxylic acid diglycidyl ester compound was first reported by Nissan chemical industry Co., Ltd, and 4-cyclohexene-1, 2-dicarboxylic anhydride was used as a raw material in W02012/017896, CN 103068876A, JP 2014-159502A, and it was alcoholyzed with allyl alcohol under acid catalysis to allyl alcohol ester. Catalysts such as concentrated sulfuric acid are used in the esterification process of allyl alcohol, so that equipment is seriously corroded, and a large amount of byproducts are generated. In addition, in the subsequent olefin epoxidation reaction, peracid (for example, m-chloroperoxybenzoic acid) is used as an oxidant for epoxidation, so that the use and purification of peracid are troublesome, and the industrial production is not facilitated.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides a method for synthesizing an aliphatic epoxy resin, which comprises the following steps:
(1) reacting conjugated olefin and maleic acid diester to obtain cyclohexene dicarboxylate;
(2) reacting cyclohexene dicarboxylate with enol to obtain cyclohexene dicarboxylate;
(3) under the action of hydrogen peroxide oxidation, cyclohexene dicarboxylic acid dialkene ester is used for obtaining the aliphatic epoxy resin.
In a preferred embodiment of the present invention, the structure of the conjugated olefin is represented by the following formula (a);
R1,R2each independently is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or R1,R2Ring closure represents an alkyl chain- (CH)2)n-, where n is 1 to 10; r3,R4,R5,R6Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
In a preferred embodiment of the present invention, the molar ratio of the conjugated olefin to the maleic diester is (0.9 to 1.1): 1.
in a preferred embodiment of the present invention, the molar ratio of the cyclohexene dicarboxylate to the enol is 1: (2-4).
As a preferred technical scheme of the present invention, the molar ratio of the cyclohexene dicarboxylic acid dialkene ester to the hydrogen peroxide is 1: (1-2).
As a preferred embodiment of the present invention, the step (1) includes: the conjugated olefin and the maleic acid diester react at the temperature of 110-130 ℃ to obtain the cyclohexene dicarboxylate.
As a preferred embodiment of the present invention, the step (2) includes: the cyclohexene dicarboxylate and the enol react to obtain the cyclohexene dicarboxylate in the presence of at least one of carbonate, organic tin substances and tetraalkyl titanate.
In a preferred embodiment of the present invention, the carbonate accounts for 0.05-2 wt% of the total amount of the cyclohexene dicarboxylate and the enol.
As a preferred embodiment of the present invention, the step (3) includes: mixing cyclohexene dicarboxylic acid dialkene ester, a solvent, a catalyst and a buffering agent, adding hydrogen peroxide, and oxidizing the cyclohexene dicarboxylic acid dialkene ester by the hydrogen peroxide to obtain the aliphatic epoxy resin.
In a preferred embodiment of the present invention, the solvent is toluene and/or 1, 2-dichloroethane.
Compared with the prior art, the invention has the following beneficial effects:
the synthetic method starts from the reaction of conjugated olefin and maleic diester, the obtained cyclohexene dicarboxylate and enol have few by-products in the reaction process, and meanwhile, the concentrated sulfuric acid does not exist, so that the corrosion of the concentrated sulfuric acid on equipment is avoided, the reaction is mild, hydrogen peroxide is used for oxidation in the subsequent epoxidation process of the cyclohexene dicarboxylate, the by-product is water, and the method is clean, environment-friendly and easy for industrial production. The epoxy resin obtained by the synthetic method has good weather resistance and can be used for outdoor paint.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a method for synthesizing aliphatic epoxy resin, which comprises the following steps:
(1) reacting conjugated olefin and maleic acid diester to obtain cyclohexene dicarboxylate;
(2) reacting cyclohexene dicarboxylate with enol to obtain cyclohexene dicarboxylate;
(3) under the action of hydrogen peroxide oxidation, cyclohexene dicarboxylic acid dialkene ester is used for obtaining the aliphatic epoxy resin.
Step (1)
In one embodiment, the conjugated olefin has the structure shown in formula (a);
R1,R2each independently is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or R1,R2Ring closure represents an alkyl chain- (CH)2)n-, where n is 1 to 10. R3,R4,R5,R6Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Preferably, R1,R2Each independently is a hydrogen atom, methane or R1,R2Ring closure represents an alkyl chain- (CH)2)n-, where n is 1 to 10.
Preferably, R3,R4,R5,R6Each independently a hydrogen atom or methane.
Preferably, said R is1-R6At least 5 of the radicals are hydrogen.
When R is1,R2Each independently is a hydrogen atom, methane or R1,R2Ring closure represents an alkyl chain- (CH)2)n-, where n is 1 to 10. R3,R4,R5,R6Each independently being a hydrogen atom or methane, especially R1-R6When at least 5 of the radicals are hydrogen, the epoxidation is complete.
In one embodiment, the molar ratio of conjugated olefin to maleic diester is (0.9-1.1): 1.
preferably, the molar ratio of the conjugated olefin to the maleic diester is 1.05: 1.
in one embodiment, the maleic acid diester is not particularly limited, and those skilled in the art can select the maleic acid diester conventionally, and diethyl maleate, dioctyl maleate, dimethyl maleate, and the like can be exemplified.
In one embodiment, the step (1) comprises: the conjugated olefin and the maleic acid diester react at 125 ℃ to obtain the cyclohexene dicarboxylate.
Step (2)
In one embodiment, the molar ratio of cyclohexene dicarboxylate and enol is 1: (2-4).
Preferably, the molar ratio of the cyclohexene dicarboxylate to the enol is 1: 3.3.
the alkenyl alcohols of the present invention are not particularly limited and may be selected conventionally by those skilled in the art.
In one embodiment, the alkenyl alcohol is allyl alcohol.
In one embodiment, the step (2) comprises: the cyclohexene dicarboxylate and the enol react to obtain the cyclohexene dicarboxylate in the presence of at least one of carbonate, organic tin substances and tetraalkyl titanate.
The organic tin-based substance is not particularly limited, and dibutyl tin dilaurate, tin octylate, and the like can be exemplified.
The tetraalkyl titanate used in the present application is not particularly limited, and tetrabutyl titanate, tetraisopropyl titanate, and the like can be used.
In one embodiment, the step (2) comprises: reacting the cyclohexene dicarboxylate with enol in the presence of carbonate to obtain the cyclohexene dicarboxylate.
Preferably, the carbonate accounts for 0.05-2 wt% of the total amount of the cyclohexene dicarboxylate and the enol; further preferably, the carbonate accounts for 0.5-1.2 wt% of the total amount of the cyclohexene dicarboxylate and enol; more preferably, the carbonate constitutes 1 wt% of the total amount of the cyclohexene dicarboxylate and enol.
The carbonate salt according to the present invention is not particularly limited and may be conventionally selected by those skilled in the art.
In one embodiment, the carbonate is potassium carbonate.
In a preferred embodiment, the step (2) comprises: cyclohexene dicarboxylate and enol react at the temperature of 100-120 ℃ in the presence of carbonate and a polymerization inhibitor to obtain cyclohexene dicarboxylate.
Preferably, the polymerization inhibitor accounts for 0.01-0.1 wt% of the total amount of the cyclohexene dicarboxylate and the enol; more preferably, the polymerization inhibitor accounts for 0.05 wt% of the total amount of the cyclohexene dicarboxylate and the enol.
The polymerization inhibitor of the present invention is not particularly limited and may be conventionally selected by those skilled in the art.
Preferably, the polymerization inhibitor is hydroquinone.
In a more preferred embodiment, the step (2) comprises: cyclohexene dicarboxylate and enol react at 110 ℃ in the presence of carbonate and polymerization inhibitor to obtain cyclohexene dicarboxylate.
Step (3)
In one embodiment, the molar ratio of the cyclohexene dicarboxylate to hydrogen peroxide is 1: (1-2).
Preferably, the mol ratio of the cyclohexene dicarboxylic acid dialkene ester to the hydrogen peroxide is 1: 1.1.
in one embodiment, the step (3) comprises: mixing cyclohexene dicarboxylic acid dialkene ester, a solvent, a catalyst and a buffering agent, adding hydrogen peroxide, and oxidizing the cyclohexene dicarboxylic acid dialkene ester by the hydrogen peroxide to obtain the aliphatic epoxy resin.
Preferably, the solvent is toluene and/or 1, 2-dichloroethane.
Preferably, the weight ratio of the solvent to the cyclohexene dicarboxylic acid dialkene ester is (0.9-1.2): 1; more preferably, the weight ratio of the solvent to the cyclohexene dicarboxylate is 1: 1.
preferably, the catalyst is a phosphotungstic heteropoly acid quaternary ammonium salt catalyst.
Preferably, the weight ratio of the catalyst to the cyclohexene dicarboxylate is 1: (50-56).
The preparation method of the phosphotungstic heteropoly acid quaternary ammonium salt catalyst is not particularly limited, and can be selected by a person skilled in the art in a conventional way.
The buffer of the present invention is not particularly limited and may be selected conventionally by those skilled in the art.
In one embodiment, the buffering agent is disodium phosphate.
Preferably, the weight ratio of the buffer to the catalyst is 100: (3-8); more preferably, the weight ratio of the buffer to the catalyst is 100: 6.
in a preferred embodiment, the step (3) comprises: mixing a solvent, cyclohexene dicarboxylic acid dialkenyl ester, a catalyst and a buffering agent, adding half of 50 wt% aqueous hydrogen peroxide, reacting at 40-55 ℃ for 0.5-1.5h, adding the rest aqueous hydrogen peroxide, reacting at 40-55 ℃ for 3-8h, cooling, standing, separating, filtering, distilling and drying to obtain the cyclohexene dicarboxylic acid dialkenyl ether.
In a more preferred embodiment, the step (3) comprises: mixing a solvent, cyclohexene dicarboxylic acid dienol ester, a catalyst and a buffering agent, adding half of 50 wt% aqueous hydrogen peroxide, reacting at 45-50 ℃ for 1h, adding the rest aqueous hydrogen peroxide, reacting at 45-50 ℃ for 5h, cooling, standing, separating, filtering, distilling and drying to obtain the cyclohexene dicarboxylic acid.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
The preparation method of the phosphotungstic heteropoly acid quaternary ammonium salt catalyst comprises the following steps: adding 20 g of tungstic acid (80mmoL) and 85mL of 30% oxygen peroxide (832.5mmoL) aqueous solution by mass percent into a reactor, stirring and heating to 60 ℃, reacting for 80 minutes, cooling to room temperature, dissolving 2.32 g of 85% phosphoric acid (20mmoL) by mass percent into 9mL of water, adding into the reaction solution, diluting the reaction solution with 180mL of distilled water, and continuously stirring for 50 minutes; dissolving 14.6 g of hexadecyl trimethyl ammonium bromide (40mmoL) in 500mL of trichloromethane, adding the solution into the reaction solution in a dropwise manner, continuing stirring for 80 minutes, standing for layering, separating out organic phase, removing the solvent in the organic phase by vacuum distillation, and drying the residue at 60 ℃ in vacuum to constant weight to obtain the phosphotungstic heteropoly acid quaternary ammonium salt catalyst, wherein the catalyst is hereinafter referred to as catalyst A.
Example 1
3.15moL of 1, 3-butadiene and 3.0moL of dimethyl maleate are added into a two-liter stainless steel reaction kettle with a polytetrafluoroethylene lining, and the reaction temperature is 125 ℃. The reaction was monitored by GC. The reaction can be carried out completely without purification and can be transferred to the next reaction. 10moL of allyl alcohol was added to the above-mentioned cyclohexene dicarboxylate, and 1 wt% of potassium carbonate and 0.05 wt% of polymerization inhibitor hydroquinone were added. The temperature was raised to 110 ℃ and excess allyl alcohol was allowed to carry over the methanol, and the progress of the reaction was monitored by GC. 690 g of cyclohexene dicarboxylate was obtained by separation by column chromatography with a yield of 92 wt%.
A2L four-necked flask was charged with 500g of toluene, 500g (2.0moL) of cyclohexene dicarboxylate, 10g of catalyst A, and 0.6g (1.68X 10 g)3moL) disodium hydrogen phosphate buffering agent, adding 74.8g of half of aqueous hydrogen peroxide (with the weight percentage concentration of 50 percent and the pure hydrogen peroxide of 1.1moL) into a reaction bottle under stirring, keeping the temperature in the reactor at 45-50 ℃, adding the rest 50 wt% of aqueous hydrogen peroxide after stirring and reacting for 1 hour, continuing to react for 5 hours at 45-50 ℃, cooling the material to room temperature after the reaction is finished, standing for 2 hours, separating an organic phase and an aqueous phase, removing water, filtering the organic phase to obtain a filter cake, obtaining a recovered phosphotungstic heteropoly acid quaternary ammonium salt catalyst, distilling the organic filtrate under reduced pressure to recover the solvent, and drying the product at 30 ℃ and 800Pa for 6 hours to obtain a transparent liquid product. The epoxy value of the product was analyzed as shown in Table 1, and the test method employed hydrochloric acid-acetone method.
Example 2
Embodiment 2 of the present invention provides a methodThe synthesis method comprises the following steps:
3.15moL of 1, 3-pentadiene and 3.0moL of dimethyl maleate are added into a two-liter stainless steel reaction kettle with a polytetrafluoroethylene lining, and the reaction temperature is 125 ℃. The reaction was monitored by GC. The reaction can be carried out completely without purification and can be transferred to the next reaction. 10moL of allyl alcohol was added to the above-mentioned cyclohexene dicarboxylate, and 1 wt% of potassium carbonate and 0.05 wt% of polymerization inhibitor hydroquinone were added. The temperature was raised to 110 ℃ and excess allyl alcohol was allowed to carry over the methanol, and the progress of the reaction was monitored by GC. 721 g of cyclohexene dicarboxylate was obtained by separation by column chromatography, 91 wt% yield.
A2L four-necked flask was charged with 528g of 1, 2-dichloroethane, 528g (2.0moL) of cyclohexene dicarboxylate, 10g of catalyst A, and 0.6g (1.68X 10)3moL) disodium hydrogen phosphate buffering agent, adding 74.8g of half of aqueous hydrogen peroxide (with the weight percentage concentration of 50 percent and the pure hydrogen peroxide of 1.1moL) into a reaction bottle under stirring, keeping the temperature in the reactor at 45-50 ℃, adding the rest 50 wt% of aqueous hydrogen peroxide after stirring and reacting for 1 hour, continuing to react for 5 hours at 45-50 ℃, cooling the material to room temperature after the reaction is finished, standing for 2 hours, separating an organic phase and an aqueous phase, removing water, filtering the organic phase to obtain a filter cake, obtaining a recovered phosphotungstic heteropoly acid quaternary ammonium salt catalyst, distilling the organic filtrate under reduced pressure to recover the solvent, and drying the product at 30 ℃ and 800Pa for 6 hours to obtain a transparent liquid product. The epoxy value of the product was analyzed as shown in Table 1, and the test method employed hydrochloric acid-acetone method.
Example 3
3.15moL of 1, 3-cyclopentadiene and 3.0moL of diethyl maleate are added into a two-liter stainless steel reaction kettle with a polytetrafluoroethylene lining, and the reaction temperature is 125 ℃. The reaction was monitored by GC. The reaction can be carried out completely without purification and can be transferred to the next reaction. 10moL of allyl alcohol was added to the above-mentioned cyclohexene dicarboxylate, and 1 wt% of potassium carbonate and 0.05 wt% of polymerization inhibitor hydroquinone were added. The temperature was raised to 110 ℃ and excess allyl alcohol was allowed to carry over the methanol, and the progress of the reaction was monitored by GC. 707 g of cyclohexene dicarboxylate is obtained by column chromatography separation, with a yield of 90 wt%.
A2L four-necked flask was charged with 528g of 1, 2-dichloroethane, 528g (2.0moL) of cyclohexene dicarboxylate, 10g of catalyst A, and 0.6g (1.68X 10)3moL) disodium hydrogen phosphate buffering agent, adding 74.8g of half of aqueous hydrogen peroxide (with the weight percentage concentration of 50 percent and the pure peroxide of 1.1moL) into a reaction bottle under stirring, keeping the temperature in the reactor at 45-50 ℃, adding the rest 50 wt% of aqueous hydrogen peroxide after stirring and reacting for 1 hour, continuing to react for 5 hours at 45-50 ℃, cooling the material to room temperature after the reaction is finished, standing for 2 hours, separating an organic phase and an aqueous phase, removing water, filtering the organic phase to obtain a filter cake, obtaining a recovered phosphotungstic heteropoly acid quaternary ammonium salt catalyst, distilling the organic filtrate at normal pressure to recover the solvent, and drying the product at 30 ℃ and 800Pa for 6 hours to obtain a transparent liquid product. The epoxy value of the product was analyzed as shown in Table 1, and the test method employed hydrochloric acid-acetone method.
Example 4
2, 3-dimethyl 1, 3-butadiene 3.15moL and diethyl maleate 3.0moL are added into a two-liter stainless steel reaction kettle with a polytetrafluoroethylene lining, and the reaction temperature is 125 ℃. The reaction was monitored by GC. The reaction can be carried out completely without purification and can be transferred to the next reaction. 10moL of allyl alcohol was added to the above-mentioned cyclohexene dicarboxylate, and 1 wt% of potassium carbonate and 0.05 wt% of polymerization inhibitor hydroquinone were added. The temperature was raised to 110 ℃ and excess allyl alcohol was allowed to carry over the methanol, and the progress of the reaction was monitored by GC. 734 g of cyclohexene dicarboxylate were isolated by column chromatography with 88 wt.% yield.
Into a 2L four-necked flask were charged 556g of 1, 2-dichloroethane, 556g (2.0mol) of cyclohexene dicarboxylate, 10g of catalyst A, 0.6g (1.68X 10)3moL) disodium hydrogen phosphate buffering agent, adding 74.8g of half of aqueous hydrogen peroxide (with the weight percentage concentration of 50 percent and the pure peroxide of 1.1moL) into a reaction bottle under stirring, keeping the temperature in the reactor at 45-50 ℃, adding the rest 50 wt% of aqueous hydrogen peroxide after stirring and reacting for 1 hour, continuing to react for 5 hours at 45-50 ℃, cooling the material to room temperature after the reaction is finished, standing for 2 hours, separating an organic phase and an aqueous phase, removing water, filtering the organic phase to obtain a filter cake, obtaining a recovered phosphotungstic heteropoly acid quaternary ammonium salt catalyst, distilling the organic filtrate at normal pressure to recover the solvent, and drying the product at 30 ℃ and 800Pa for 6 hours to obtain a transparent liquid product. The epoxy value of the product was analyzed as shown in Table 1, and the test method employed hydrochloric acid-acetone method.
Example 5
3.15moL of 2, 4-hexadiene and 3.0moL of diethyl maleate are added into a two-liter stainless steel reaction kettle with a polytetrafluoroethylene lining, and the reaction temperature is 125 ℃. The reaction was monitored by GC. The reaction can be carried out completely without purification and can be transferred to the next reaction. 10moL of allyl alcohol was added to the above-mentioned cyclohexene dicarboxylate, and 1 wt% of potassium carbonate and 0.05 wt% of polymerization inhibitor hydroquinone were added. The temperature was raised to 110 ℃ and excess allyl alcohol was allowed to carry over the methanol, and the progress of the reaction was monitored by GC. 792 g of cyclohexene dicarboxylate is obtained by column chromatography separation with a yield of 95 wt%.
Into a 2L four-necked flask were charged 556g of 1, 2-dichloroethane, 556g (2.0moL) of cyclohexene dicarboxylate, 10g of catalyst A, 0.6g (1.68X 10)3mol) disodium hydrogen phosphate buffer, half of the buffer being added with stirring74.8g of aqueous hydrogen peroxide (with the weight percentage concentration of 50 percent and the pure peroxide of 1.1moL) is put into a reaction bottle, the temperature in the reactor is kept between 45 and 50 ℃, the residual aqueous hydrogen peroxide of 50 percent by weight is added after the reaction is carried out for 1 hour by stirring, the reaction is carried out for 5 hours under the condition of the temperature between 45 and 50 ℃, after the reaction is finished, the material is cooled to the room temperature, the material is kept stand for 2 hours, an organic phase and an aqueous phase are separated and water is removed, the organic phase is filtered to obtain a filter cake, the recovered quaternary ammonium phosphotungstic heteropoly acid catalyst is obtained, then the organic filtrate is distilled at normal pressure to recover the solvent, and the product is dried for 6 hours at the temperature of 30 ℃ and 800Pa to. The epoxy value of the product was analyzed as shown in Table 1, and the test method employed hydrochloric acid-acetone method.
Example 6
3.15moL of 1, 3-cyclohexadiene and 3.0moL of diethyl maleate are added into a two-liter stainless steel reaction kettle with a polytetrafluoroethylene lining, and the reaction temperature is 125 ℃. The reaction was monitored by GC. The reaction can be carried out completely without purification and can be transferred to the next reaction. 10moL of allyl alcohol was added to the above-mentioned cyclohexene dicarboxylate, and 1 wt% of potassium carbonate and 0.05 wt% of polymerization inhibitor hydroquinone were added. The temperature was raised to 110 ℃ and excess allyl alcohol was allowed to carry over the methanol, and the progress of the reaction was monitored by GC. 795 g of cyclohexene dicarboxylate is obtained by column chromatography separation, with a yield of 96 wt%.
Into a 2L four-necked flask, 552g of toluene, 552g (2.0moL) of cyclohexene dicarboxylate, 10g of catalyst A, 0.6g (1.68X 10 g) of catalyst A were charged3moL) disodium hydrogen phosphate buffer, adding 74.8g of half of aqueous hydrogen peroxide (50 wt% concentration, 1.1moL of pure oxygen peroxide) into a reaction bottle under stirring, keeping the temperature in the reactor at 45-50 ℃, adding the rest 50 wt% aqueous hydrogen peroxide after stirring for reaction for 1 hour, continuing to react for 5 hours at 45-50 ℃, cooling the material to room temperature after the reaction is finished, standing for 2 hoursSeparating an organic phase and a water phase, removing water, filtering the organic phase to obtain a filter cake, obtaining a recovered phosphotungstic heteropoly acid quaternary ammonium salt catalyst, distilling the organic filtrate at normal pressure to recover the solvent, and drying the product at 30 ℃ and 800Pa for 6 hours to obtain a transparent liquid product. The epoxy value of the product was analyzed as shown in Table 1, and the test method employed hydrochloric acid-acetone method.
Example 7
3.15moL of 1-methyl-1, 3-cyclopentadiene and 3.0moL of diethyl maleate are added into a two-liter stainless steel reaction kettle with a polytetrafluoroethylene lining, and the reaction temperature is 125 ℃. The reaction was monitored by GC. The reaction can be carried out completely without purification and can be transferred to the next reaction. 10moL of allyl alcohol was added to the above-mentioned cyclohexene dicarboxylate, and 1 wt% of potassium carbonate and 0.05 wt% of polymerization inhibitor hydroquinone were added. The temperature was raised to 110 ℃ and excess allyl alcohol was allowed to carry over the methanol, and the progress of the reaction was monitored by GC. 704 g of cyclohexene dicarboxylate was obtained by column chromatography with a yield of 85 wt%.
Into a 2L four-necked flask, 552g of toluene, 552g (2.0moL) of cyclohexene dicarboxylate, 10g of catalyst A, 0.6g (1.68X 10 g) of catalyst A were charged3moL) disodium hydrogen phosphate buffering agent, adding 74.8g of half of aqueous hydrogen peroxide (with the weight percentage concentration of 50 percent and the pure hydrogen peroxide of 1.1moL) into a reaction bottle under stirring, keeping the temperature in the reactor at 45-50 ℃, adding the rest 50 wt% of aqueous hydrogen peroxide after stirring and reacting for 1 hour, continuing to react for 5 hours at 45-50 ℃, cooling the material to room temperature after the reaction is finished, standing for 2 hours, separating an organic phase and an aqueous phase, removing water, filtering the organic phase to obtain a filter cake, obtaining the recovered phosphotungstic heteropoly acid quaternary ammonium salt catalyst, distilling the organic filtrate at normal pressure to recover the solvent, and drying the product at 30 ℃ and 800Pa for 6 hours to obtain a transparent liquid product. The product was analyzed for epoxy value, see Table 1, test methodsBy the hydrochloric acid-acetone method.
TABLE 1
Examples | Epoxy value in units (moL/100g) |
Example 1 | 0.90 |
Example 2 | 0.89 |
Example 3 | 0.89 |
Example 4 | 0.62 |
Example 5 | 0.85 |
Example 6 | 0.87 |
Example 7 | 0.88 |
As is clear from the measurement of the epoxy value, in examples 1 to 3, 5 to 7, three olefins were substantially epoxidized, and a small part of the double bonds were not epoxidized or ring-opened. Example 4 since the double bond of the cycloolefin is substituted with a substituent, the steric hindrance is large, and the epoxidation of the olefin is difficult to occur, and the epoxy value is measured to be 0.62.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A method for synthesizing aliphatic epoxy resin is characterized by comprising the following steps:
(1) reacting conjugated olefin and maleic acid diester to obtain cyclohexene dicarboxylate;
(2) reacting cyclohexene dicarboxylate with enol to obtain cyclohexene dicarboxylate;
(3) under the action of hydrogen peroxide oxidation, cyclohexene dicarboxylic acid dialkene ester is used for obtaining the aliphatic epoxy resin.
2. The method for synthesizing an aliphatic epoxy resin according to claim 1, wherein the structure of the conjugated olefin is represented by the following formula (a);
3. The method for synthesizing an aliphatic epoxy resin according to claim 2, wherein the molar ratio of the conjugated olefin to the maleic diester is (0.9-1.1): 1.
4. the method for synthesizing aliphatic epoxy resin according to claim 1, wherein the molar ratio of the cyclohexene dicarboxylate to the enol is 1: (2-4).
5. The method for synthesizing the aliphatic epoxy resin according to claim 1, wherein the molar ratio of the cyclohexene dicarboxylate to the hydrogen peroxide is 1: (1-2).
6. The method for synthesizing an aliphatic epoxy resin according to any one of claims 1 to 5, wherein the step (1) comprises: the conjugated olefin and the maleic acid diester react at the temperature of 110-130 ℃ to obtain the cyclohexene dicarboxylate.
7. The method for synthesizing an aliphatic epoxy resin according to claim 6, wherein the step (2) comprises: the cyclohexene dicarboxylate and the enol react to obtain the cyclohexene dicarboxylate in the presence of at least one of carbonate, organic tin substances and tetraalkyl titanate.
8. The method for synthesizing aliphatic epoxy resin according to claim 7, wherein the carbonate accounts for 0.05-2 wt% of the total amount of the cyclohexene dicarboxylate and the enol.
9. The method for synthesizing an aliphatic epoxy resin according to claim 7 or 8, wherein the step (3) comprises: mixing cyclohexene dicarboxylic acid dialkene ester, a solvent, a catalyst and a buffering agent, adding hydrogen peroxide, and oxidizing the cyclohexene dicarboxylic acid dialkene ester by the hydrogen peroxide to obtain the aliphatic epoxy resin.
10. The method for synthesizing an aliphatic epoxy resin according to claim 9, wherein the solvent is toluene and/or 1, 2-dichloroethane.
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